Method of depositing on chromium



Aug. 16, 1932. Y B. BART 1,8%,770

METHOD OF DEPOSITING ON CHROMIUM I Filed Aug. 24, 1929 Ta. Z.

BLASR US' BART ATTORNEY Patented Aug. 16, 1932 UNITED STATE-sv PATENT OFFICE BLASIUS BART, OF EAST OILANGE, JERSEY, ASSIGNOR TO T HE FRINK CORPORA- TION, OF LONG ISLAND CITY, NEW YORK, A CORPORATION OF DELAWARE 'METHOD DEPOSITING 0N' CHROMIUM l 4applicati@ mea Agust 24, 1929.4 serial N V388,231,

The invention relates in general to an Iimprovement in the art of forming articles by electrolytic precipitation and the invention particularly relates to the art of producing three dimension facsimiles, such as parabolic reflectors accurate to molecular proportions and which are required, to have a capacity to reflect the' greatest amount of light imposed' on the same or parts of the saine. 'if' The invention relates to an improvement in the method of forming metallic reflectors and similar articles by electrolytic deposition and particularly in the method of forming Working molds on Which said reflectors and other finished articles are formed, and the inven- .tion also relates to apparatus designed for use' in practicing such methods.

It has been regarded in the art as necessary heretofore that such molds be formed of glass for no other material apparentlyl could be produced which would give the requisite smoothness of surface and at the same time even approach the reguisite accurately dened surface capable o receiving the electro# lytic precipitation of the mold which was to form thereflecting and other desired configuration of surface. The cost of producing glass molds is well nigh'prohibitive lue to cost of accurate grinding and glass molds cannot be produced accurately at a price which will insure'a satisfactory manufacturing product. Glass, molds have otheroba jectionable feature`s they develop a porous surface and after repeated resilverig chips break away from the silver surface.

Efforts have been made to meet this prob lem by the use of metal molds but thes'V attempts have failed, among other reasons, due to the fact that it was necessary to expend much labor in polishing each maid. Polishing is often responsible for modifications sufficient to destroy the re uisite form of the finally finished article. urther corroding and oxidizing quickly aEected the light reflecting character of such known metal surfaces after they had been in use for some time. At-` tempts have been made to protect these metal surfaces from corroding and from other deteriorating action usually by coating them with some form of lacquer, sometimes with Wax or other thin medium, butsuch coating y i seriously affected the appearance ofthe resultin surface so that the desired `hrilliancy of reacting surface could not be obtained. Besides any such method which added something to the mold surface had the disadvantage in that each mold had to be coated or otherwise treated after each succeeding rse,y

thus adding to manufacturing costs.

Accordingly, the primary object of the inf vention is to provide a method of procedure for forming accurately defined reflectors and other articles, particularly those which require brilliant reflecting surfaces, and at the same time, to avoid the abjections which have heretofore been inherent in the use of` glass and metal molds. Differently expressed,V s

the-invention features a method for reproducing accurately a large number of reflectors or other articles particularly tridimensional articles, each of which will be an exact facsimile uof the other and each corresponding exactly to the surface characteristics, proportions and configurations of a master mold.

Still another object of the invention is lto provide a working mold as an exact fac'h simile of the master mold and which Working mold maybe retained practically indefinitely with a non-corroding, non-oxidizing sur- 9 face havmg the smoothness characterizing a highly'polished metallic surface and which i mold can be used repeatedly Without necessity of repolishing or retreating it in any Way between succeeding uses.

Broadly, these objects are attained by depositing, electrolytically, on a highly polished master mold, a layer of non-corroding fine grain metal, such as chromium, positioning a backing layer on the chromium layer to form a working mold and if desired, duplicating this process until any desired number ofjworking molds are formed from the master mold. Theworking molds so produced are used rcpeatedly as cathodesin electrolytic baths to form facsimiles of the master mold. It is a feature of this disclosure that after once being subjected toa hydrogenizing treatment these working molds are used repeatedly without necessity of any subsequent or intermediate treatment.

The invention also features the use of insulating means for blocking off the deposits from portions of such working molds on which deposits are not desired; the providing of means for preventing laking or peeling koff of the' metallic layers deposited on the working mold and for temporarily retaining the depositedlayer on the mold until the requisite thickness ofdeposit is attained.

Various other objects and advantages of i the invention will be in part obvious from a ,6.0. as is illustrated in Fig. l and the preparation consideration of the method features of the disclosure and from an inspection of the accompanying drawing and in part will be more fully set forth in the following particular description of one method of practicing the invention,and the invention also consists in certain new and novel modifications of the preferred method and other features of constructionl and combinations of parts hereinafter set'forth and claimed.

In the accompanying drawing, t,

Fig. 1 is a vlew llargely in diagrammatic outline of a master mold shown in axial section and illustrating apparatus for use in the method of forming the working mold herein featured;

Fig. 2 is a view partly in side elevation and partly in section, of a working mold formed in part on the master' mold shown in Fig. 1 and illustrating the metallic part of the mold without the-insulating' blocking off features;

Fig. 3 is a view similar to Fig. 2 showing the mold of Fig. 2 in the next succeeding step.

in the method with an initial part of the final article forming layer and with the insulatin blocking oif elements in place;

i 4 is an enlarged detailed view showing t e lowerl portion of Fig. 3 and showing the1 nal stage of the metal depositing step; an

Fig. 5 is a view in perspective of a metallic reflector constituting the product produced by following the method herein featured and with part of the securing flange shown in Fig. 4 cut away. l

ofthe original mold must be done carefully and with suchcaution as to give the accuracy 'deis-'fired in the resulting reflectors and other facsimiles made therefrom. However, after the first master mold has been completed, the

approved practices known in this art. It

herein suggestedthat the master mold 10 be formed of a non-fusible metal, preferably a fine grain iron o'r tool steel, or, preferably, it may be made of electrolytically deposited nickel. It is also suggested that other metals can be used as well as non-,metallic substances such as Celluloid. In any case', the mold 10 has a deposit receiving surface 11 accurately defined to form the -complement of the surface to be'reproduced. It is a feature of this disclosure that such surface must lbe highly polished, particularly Where vit isto define the brilliancy of the resultingV reflecting surface. The master mold thus produced and polished is designed and constructed with the necessary supporting parts in order to constitute the cathode element in an electrolytic bath to receive thereon a deposit of metal which will constitute eventually the metal receiving surface of the working mold. This metal deposit may be, or may form part of, the reflector or other final article desired to be produced, but betterV results are attained, especially when large numbers of facsimiles are to be produced, when the master mold is used simply to form other molds hereinafter referred to as working molds. and such other working molds ma be utilized to form the final article.

he master mold is positioned in an electrolytic tank containing an electrolyte capable of forming a non-corroding, brilliant refiecting surface. While several metals may be used, such as platinum or any metal of the platinum group, it has been found that the best practical results are obtained by using the metal chromium in the solution. In this way there is produced a chromium shell 12`such as is shown' in Fig. 2, which is preferably formed as an extremely thin layer of the order of about 0.001 to 0.005 of an inch. On this chromium layer, while in en. gagement with the master mold, there is formed a backing or strengthening layer of any approved form. It is herein-suggested that a backing layer 13 be formed of nickel deposited electrolytically and of a thi. ckness to -give suiiicient ri idity to the mold so as to maintain its con guration when removed frpm the master mold. -In the particular form herein selected for illustration, the working mold includes the layer 13 hereinafter referred to as a form with its thin chromium facing 12. The form is of a dish or hat shaped configuration and comprises la central curved parabolic portion 14 outlined b. a. Z-shape 15. The Z-shape is formed in e ect byman inner flange 16 constitutingA a.'

'flanged edge to the parabolic portion 14 and an outer flano'e 17. The two fianges extend in parallel planes and are connected by an intermediate rim or transverse fiange 18 concentrically disposed relative to the axis a-p-b of the parabolicportion 14. It will be understood that this peculiar configuration is due to the corresponding configuration of the recess portions 19 of the master mold'1`0.

The working mold as thus far completed has positioned on its rear face a'layer of insulating material 20 designed to constitute a means for blocking ofl' the deposition from forming on the rear side of the mold. This layer 20 may be a layer of hard rubber or celluloid, permanently fixed to the form -13 following conventional practices in this re-y spect, but ispreferably a removable sheet of some suitable form of insulating material temporarily held to the form by cement or other suita le fastening means.

It is understood thatthe layer 12 of chromium is intentionally made thin and any such thin layer is quite apt to bedissolved if subjected for any material length of timel to the action of certain electrolytes in which it is intended that the mold shall be used in producing the finished article. It is also a fact that certain metals, suchas silver, when deposited on the chromium faced mold, develops a tendency, particularlyduring the initial part of the depositing operation, to fail to adhere to the chromiuitn,` face of the mold. In order to insurerthe'maintenance of the deposited layer on the chromium sired on the finished article. This metal may be silver, nickel, cooper, or any other metal usually usedin electrolytic baths. In the instant case, it is to be understood that a metal is used which is of a fine grain texture, ca-

pable of producing a highly refiective surface. Silver or palladium or the alloy disclosed in my pending application Serial No. 283,997 filed June 8, 1928, is suggested.

The first time the Working mold is used and when in the form shown in Fig. 2, it is 'subjected to a hydrogenizing treatment, but it is .a feature of this disclosure that after the mold has been once subjected to this hydrogenizing treatment, it can be used repeatedly without necessity of any subsequent similar treatment. A

It is suggested that the hydrogenizing treatment consists in positioning the chromium faced working mold shown in Fig. 2

n, to the action of an electrolytic bath containing three to tenl percent normal solution of sulphuric acid for a period of about ten to thirty seconds; in the presence of current at 6 to.12 volts and with 20 to 5.0 amperes per square foot. Another and quicker method which is not as effective, is to dip the mold into dilute hydrochloric acid for a second or two.

With the mold having its surface so hydrogenized and" withthe backing layer 20 in place as shown in Fig. 3, it is subjected to the action of the electrolytic bath for a shortAtime, usually a couple of minutes in the case 'of silver, until an extremely thin initial layer 22 "is formed on the exposed face of the mold as particularly shown in Fig.

,3 and on the iange 17 of Fig. 4. It will be noted that this-thin layer extends not only across the' parabolic portion and along the fiange 16 but also extends along the stepped portion formed by the flanges 17 and 18 and across the outer edge 23 of the flange 17 up to the insulating backing layer 20.

AWhen this layer, in the instantcase tlfe silver layer, is thus formed, the mold is removed from the tank and a soft rubber split ring 24 is disposed in position encircling the flange 17 and resiliently clamping the edge of the thin metal layer '22 to the mold facing layer 12 on the exposed side of the flange 17. This rubber ring acts not Aonly to hold the layer 22 to the mold but also acts as a means for stopping off'subsequent deposits on the portion of the layer 22 positioned `within and protected by the insulating ring 24. With this. ring in place, the mold is replaced in the electrolytic tank, in this case the copper tank, and the depositing operation continued until a layer 25 of any desired thickness has formed on top of and integrally connected with the initial layer 22. The inner edge 26 of the ring 24 sharply defines the relatively thick portion of the layer 25 and there is'avoided the usual accumulation of deposited metal which has a tendency to collect at the place corresponding tothe point 26 when other forms of blocking means, such as metallic conductors are used at this place.

When the desired thickness of material 25 is attained, the ring 24 is removed and as ordinarily the formed shell as'shown in Fig. 5 will be held by .suction to the mold, it will be necessary to break the suction effect by prying away the thin edge of the initially deposited portion 22 engaging the flange 17 or otherwise conventionally separate the fin-` ished shell from the mold. The surplus material in the flange 27 is cut away along the line 21 and there is finally produced the reflector shown in Fig. 5 with the fiange 27 removed after which the outstanding fiange 28 may be suitably drilled to provide fastening apertures 29.

It is Within the scope of this disclosure to deposit a layer of chromium, silver or other suitable metal on the initial layer 12 to any desired thickness and thereafter any suitable metal such as copper may be deposited electrolytically on the chemically `laid chromium or silver as herein finishing the article. l

In pr`actice, it has been found that the working mold can be used for a hundred or more times Without any treatment between succeeding uses. Eventually, the brilliant polish-like surface vat 12 begins to show Wear and otherwise becomes deteriorated to an eX- tent such that the reflective surfaces 30 on the reproduced shells begin to-lose their brilliancy or otherwise depart from the characteristics of'the mold. Should the surface 12 simply become slightly scratched either during use or at thetime it Was removed from the mold 10, itis suggestedthat the defective portion might be polished as is usual with polished -inetal surfacesbut it is a feature of this disclosure that the chromium tioned in the chromium containing electro-` lytic bat l lytically, the method whic face of the .mold is not polished and in fact 1t is prescribed that 4the working mold be not touched in anyway 'after its removal from the --master mold except for the initial hydrogenizing treatment above outlined.

When the chronium surface becomes Worn, damaged or otherwisedeleteriously affected, itjmay be readily dissolved by positioning the mold Without its backing 20 or ring 24, for a short time in a solution of hydrochloric 'acid after which the resulting form 13 With the insulating backing 20 thereonl isposiand the chromium surface 'reformed.V As the -chromium layer is extremely thin, the surface refinished will be identical with the similar surfaceq when formed initially on the master fmold.

,While I have shown and described, and havepointed out in the annexedclaims, certain novel features `of the invention, `it will be understood that various omissions, substitutes-and changes in the form anddetails of the device illustrated and in its dperation may be made by those skilled in the artvvithout departing from the spiritof the invention.

l.. In the art of formin Aarticles electroconsists in providing a` master mold havinga highly polished metallic surface, subjecting the same to the action of an electrolytic bath 4 containing chromiumto form on said highly polished surface a thin layer of chromium having a surface exactly the complement of the highly polished master mold surface and possessing the highly polished light reflecting characteristics of such'surface, forming a backing layer of metal on said thin chromium layer to form a Working mold, posiindicated in y tioning a layer of insulating material on said backing layer leaving the edge and the chromium faced surface of the Working mold exposed, subjecting the Working mold with one side'so insulated to the action of an electrolytic bath until a'thin initial coating of metal has formed on the exposed surface, positioning a ring of resilient insulating material about the edge of the Working mold to block off further deposits 'thereon and to clamp the edge of the initial coating'to the ch-romium surface, continuing to subject ther Working mold Withits initial layer of metal so clamped to the action of said electrolytic bath until the layer is of the desired thickness, removing the clamping ring, removing the formed layer from the Working mold and trimming olf the portion of the initial layer' which was covered by the ring.

v2. In the art of forming metallic reflectors and other articlescharacterized by having portions with highly reflective surfaces, the

method which consists in forming a thin layer of chromium on afhighly polished master mold, backing said layer to form a Working mold, subjecting the chromium sur- D face to a hydrogenizing treatment,`subject ing the Working mold with its chromium surface so treatedto the action of an elect-rolytic bath to form thereon a thin -initial layer of metal capable of forming a brilliant reflective surface, temporarily securing said thin layer to the Working mold and`continuing to subject it to the action.,v of the electrolytic bath until the desired thickness of metal is attained, and removing the securing means to permit thelayer to be'separated from the chromium surfaced Working mold.

3. In the art of producing .three dimension facsimiles accurate to molecular proportions, the method, which consists in providing a mold having a surface the complement of the surface to be reproduced, said'mold surface defined -by a layer of chromium initially subjecting said chromium surface to the action of an electrolytic bath containing a solution of\ 'sulphuric acid and successively lsubji-:cting said surface to the action of an electrolytic'bath to form thereon layers of metal, one after the other, ivithout' intermediate treatment of the mold between succeed" repeating said deposition action without any treatment of the chromium mold surface between the succeeding depositions thereon of the metal layers. i

' 5. In the art of forming articles electrolytically, the method which consists in forming a layer of chromium electrolytically on a master mold having a highly polished deposit receiving surface, subjecting said chromium layer used as a working mold to the action of an electrolytic bath to form thereon a thin initial layer of metal, mechanically clamping said metal layer at its edge to the chromium layer to hold the same temporarily in place. blocking off further depositions at said clamped edge while exposing other portions of the initial layer and continuing to subject said initial layer while clamped to the chromium layer to the actionof the electrolytic bath until said other exposed portion of the met-al layer has reached the desired thickness and removing said layer so formed from the working mold.

6. In the art 0f forming fianged reflectors electrolytically, the method which consists in forming initially a `thin layer of metal on a working mold, mechanically clamping said llayer to the mold at said shouldered portion by means which will act to block off succeeding deposits from the portion of the layer so clamped, continuing to subject the exposed portions of the layer to the action of said rial, and the opposite side of said mold be ing of a conducting material and annular means including the exposed edge of the outer iiange for stopping off deposits on the side faces of the outer flange while permitting the forming of a deposited layer on the face of the mold defined by the conducting material and within the outlines of said annular means.

8. A Working mold for use in an electrolytic bath, comprising a hollowr metal form having a curved side thereof faced with a layer of electrolytic metal and the other side faced with a removable layer of insulating material, and insulating means for closing the joint between the electrolytic metal face and the layer of insulating material.

9. In a device for use as a cathode in an electrolytic bath, the combination of a mold with one side thereof defined by a conducting material and the other side defined by an in- 'sulating material, and having an outlining edge, and an annular ring of insulating material demountably positioned on the mold enclosing said outlining edge and acting to stop olf deposition from forming at said edge while leaving the portion of the conducting Vsurface within said ring exposed for receivling thereon an electrolytic deposit.

10. In a device for use as a cathode in an electrolytic bath, the combination of a mold having an outlining edge and a deposit receiving surface, an elastic ring of insulating material enclosing said edge in clutching engagement WithA the mold and acting to define the outlining edge of the deposit formed on said surface. Y I 11. A working mold for use in an electrolytic bath comprising a nickel form having on one side thereof a layer of electrolytically deposited chromium and .having the other side faced with a layer of insulating material and a soft rubber ring encircling the mold and enclosing the edges of said layer.

l2. A- mold for use in forming flanged parabolic reectors, comprising a metal form having a central parabolic portion outlined by an outstanding flanged portion one side of said form defined by a layer of electrolytically deposited and easily removable metal, the opposite side defined by a layer of insulating material, and a ring of elastic and insulating material adapted to be disposed in position encircling the flanged portion for enclosing the edges of the mold and for securing thereto deposits formed on the layer of metal prior to positioning the ring in place.

Signed at New York in the county of New York and State of New York, this 15th day of August, A. D. 1929. A BLASIUS BART. 

